BR112020002051A2 - composition of protective curable surface coating, processes for its preparation and application to a metallic substrate and resulting coated metallic substrate - Google Patents

Abstract

The present invention relates to a surface protective coating formation composition that exhibits excellent shelf life (storage stability) and the performance of the cured coating is derived from trialoxysilane and metal oxide powder.

Description

“COMPOSITION OF PROTECTIVE COATING OF CURABLE SURFACE, PROCESSES FOR ITS PREPARATION AND APPLICATION TO A METALLIC SUBSTRATE AND RESULTED COATED METALLIC SUBSTRATE ” FIELD OF THE INVENTION

[001] The present invention relates to the field of surface protective coating compositions, for example, conversion and passivation coatings and, more particularly, to curable coating compositions derived from alkoxysilanes and processes for coating metallic substrates with the same .

HISTORY OF THE INVENTION

[002] Numerous protective surface coating compositions have been developed over the years for application to various types of surfaces with the purpose of imparting anti-corrosion and / or anti-wear properties to it. For example, chromium and heavy metal phosphate conversion coatings were used to prepare metal surfaces before painting. However, growing concerns about the toxicity of chromium and the polluting effects of chromates, phosphates and other heavy metals discharged into streams, rivers and other waterways as industrial waste have spurred the search for alternatives to such metal coating compositions.

[003] A type of surface protective coating composition that emerged from these efforts to develop non-chromium, non-phosphate and non-heavy metal coating compositions is derived from alkoxysilanes.

Although curable coating compositions derived from alkoxysilanes continue to attract a high level of interest within the metal industry with some formulations having achieved wide commercial acceptance, there remains considerable room for improvement in one or more of these properties which continue to be of great importance to manufacturers and metal processors, for example, storage stability of uncured compositions and adhesion, flexibility, corrosion resistance, abrasion / wear resistance and optical clarity properties of cured compositions.

SUMMARY OF THE INVENTION

[004] According to one aspect of the invention, a curable surface protective coating formation composition is provided for application to protect the surface of a substrate such as a metal, metal alloy, metal part, metal part or metallized having one or more protective layers, the coating formation composition comprising: (i) at least one alkoxysilane selected from the group consisting of Formulas A and B: (X-R1) to Si (R2) b (OR3) 4- ( a + b) Formula A (R3O) 3Si-R1-Si (OR3) 3 Formula B where: X is an organofunctional group, more specifically a mercapto, acyloxy, glycidoxy, epoxy, epoxycyclohexyl, epoxycyclohexylethyl, hydroxy group , episulfide, acrylate, methacrylate, ureide, thioureide, vinyl, ally, -NHCOOR4 or -NHCOSR4 in which R4 is a monovalent hydrocarbyl group containing from 1 to about 12 carbon atoms, more specifically from 1 to about 8 carbon atoms , thiocarbamate group, dithiocarbamate, ether, thioether, disulfide, trisulfide, tetrasulfide, pentasulfide, hexasulfide, polysulfide, xanthate, tritiocarbonate, dithiocarbonate or isocyanurate or other group -Si (OR3) where R3 is as defined below; each R1 is a linear, branched or cyclic divalent organic group of 1 to about 12 carbon atoms, more specifically from 1 to about 10 carbon atoms, and more specifically from 1 to about 8 carbon atoms, for example, a divalent hydrocarbon group such as the non-limiting examples of methylene, ethylene, propylene, isopropylene, butylene, isobutylene, cyclohexylene, arylene, aralkylene or alkylene group and optionally containing one or more heteroatoms such as the non-limiting examples of O, S and NR4 in which R4 is hydrogen or an alkyl group of 1 to 4 carbon atoms;

each R2 is independently alkyl, aryl, alkaryl or aralkyl group of

1 to about 16 carbon atoms, more specifically from 1 to about 12 carbon atoms, and even more specifically from 1 to 4 carbon atoms, and optionally containing one or more halogen atoms, more specifically a fluorine atom;

each R3 is independently an alkyl group of 1 to about 12 carbon atoms, more specifically from 1 to about 8 carbon atoms and even more specifically from 1 to 4 carbon atoms;

a subscript is 0 or 1, b subscript is 0, 1 or 2 and a + b is 0, 1 or 2; and,

the amount of alkoxysilane of Formula A when a subscription is 0 or

1, subscript b is 0, 1 or 2 and a + b is 2 is 0 to about 8 weight percent of the coating formation composition,

the amount of alkoxysilane of Formula A when a + b is 0 is from 0 to about 15 weight percent of the coating formation composition,

the combined amounts of Formula A alkoxysilane in which a subscript is 0 or 1, b subscript is 0 or 1 and a + b is 1 and Formula B alkoxysilane is about 8 to about 40 weight percent, and the total amount of alkoxysilane of Formulas A and B does not exceed about 50, preferably about 45, more preferably about 40 weight percent of the coating formation composition;

(ii) at least one metal oxide in particulate form, the amount of metal oxide being about 5 to about 50 weight percent of the coating formation composition;

(iii) at least one water-miscible organic solvent;

(iv) at least one acid hydrolysis catalyst;

(v) water; and,

(vi) optionally, at least one condensation catalyst,

the coating formation composition having a viscosity at 25 ° C within the range of about 3.0 to about 7.0 cStks, more specifically from about 4.0 to about 5.5 cStks and even more specifically about 4.5 to about 5.0 cStks.

[005] In the present invention, viscosity is measured at 25 ° C according to DIN 53015, "Viscometry - Measurement of Viscosity by Means of the Rolling Ball Viscometer by Hoeppler" using a Hoeppler Model 356 drop viscometer -001 equipped with a Haake DC10 temperature control unit and set of balls 800-0182, in particular ball n ° 2 having a diameter of 15,598 mm, a weight of 4.4282 g and a density of

2,229 g / cm3.

[006] In one embodiment of the invention, the at least one alkoxysilane (i) selected from the group consisting of Formulas A and B can also be hydrolyzed and condensed products thereof.

[007] Such oligomers of alkoxysilane (i) selected from the group consisting of Formulas A and B and the like. They are prepared by hydrolysis and condensation of the alkoxysilanes (i) selected from the group consisting of Formulas A and B. That is, the alkoxysilyl groups react with water, releasing the corresponding alcohol and then the resulting hydroxysilyl groups condense with the formation of Si -O-Si (siloxane groups). The resulting hydrolyzed and condensed products or oligomers can be, for example, linear or cyclic polysiloxanes comprising from 2 to 30 siloxy units, preferably from 2 to 10 siloxy units and the remaining alkoxy groups.

[008] It should be understood that the conditions relating to the amounts of alkoxysilanes (i), that is, the amount of alkoxysilane of Formula A when a subscript is 0 or 1, b subscript is 0, 1 or 2 and a + b is 2 is from 0 to about 25 weight percent of the coating formation composition,

the amount of Formula A alkoxysilane when a + b is 0 is 0 to about 15 weight percent of the coating formation composition, the combined amounts of Formula A alkoxysilane in which a subscript is 0 or 1, b subscript is 0 or 1 and a + b is 1 and the alkoxysilane of Formula B is about 8 to about 40 weight percent of the coating formation composition, and the total amount of alkoxysilane of Formulas A and B does not exceed about of 50, preferably about 45, more preferably about 40 weight percent of the coating formation composition, also apply to the corresponding oligomers that are derived from the alkoxysilane of Formulas A and B.

Preferred specific examples of such oligomers include in particular oligomeric glycidoxypropyl trimethoxysilane.

[010] Still in accordance with the present invention, there is also provided a process for forming the above curable surface protective coating formation composition comprising: a) cooling a mixture of alkoxysilane (s) (i) and a portion of acid hydrolysis catalyst (iv); b) adding metal oxide (ii) and water (v) to the cooled mixture from step (a); c) adding organic water-miscible solvent (iii) and the remainder of acid hydrolysis catalyst (iv) to the mixture resulting from step (b); d) aging the mixture resulting from step (c) under high temperature conditions and for a period of time effective to provide a curable coating formation composition having a viscosity at 25 ° C within the range of about 3.0 to about from 7.0 cStks, more specifically from about 4.0 to about 5.5 cStks and even more specifically from about 4.5 to about 5.0 cStks; and e) optionally, adding the condensation catalyst (vi) in, during or after, any of the previous steps.

[011] This process is particularly preferred when metal oxide (ii) is a colloidal suspension of at least one metal oxide selected from the group consisting of silica, alumina, titania, ceria, tin oxide, zirconia, antimony oxide , indium oxide, iron oxide, titania doped with iron oxide and / or zirconia and rare earth oxide, or when metal oxide (ii) is selected from a mixture of alumina and silica.

[012] Still according to another embodiment of the present invention, there is also provided a process for forming the anterior curable surface protective coating composition comprising: cooling a mixture of the metal oxide (ii) and the hydrolysis catalyst acidic (iv) preferably up to a temperature of about -20oC to about 15oC, preferably of about -10oC to about 10oC, more preferably from about 0 to about 10oC, addition of alkoxysilane (i) ( or a mixture thereof) to the cooled mixture from step (b); allowing the mixture obtained in step c) to warm to room temperature (approximately 25 ° C) (preferably by letting it reach room temperature, for example, overnight or less preferred by providing heat), adding at least a water-miscible organic solvent (iii), and optionally the condensation catalyst (vi) and optionally one or more other optional components (vii) to the mixture obtained in step d) to obtain a composition having a viscosity within the range of about 3.0 to about 7.0 cStks at 25 ° C. This process is particularly preferred when the metal oxide (ii) is selected from silica modified with alumina. For example, a mixture of modified silica with alumina particles such as Levasil® 100S / 45 (now: Levasil CS45-58P) (AkzoNobel) and Levasil® 200S / 30 (now: Levasil CS30-516P) (AkzoNobel) and acetic acid (iv) is shaken in a flask. The mixture is cooled to 0 - 10 ° C while the alkoxysilanes (i) are added in drops within 20 -

50 min The mixture is stirred while the solution is allowed to reach room temperature. The next day, solvents (iii) such as alcohols, catalyst (vi) and flow additive (vii) are added. The entire mixture is stirred for at least 15 min to obtain a coating formation composition.

[013] According to yet another aspect of the invention, a metal that has a protective surface coating, that is, a coating that imparts corrosion resistance and / or abrasion resistance to an uncoated or pre-coated metal surface. , is obtained by the coating process which further comprises: f) applying a coating of the above coating formation composition to an uncoated or precoated surface of a metal; g) removing at least some solvent (iii) from the applied coating of the coating formation composition; and h) curing the solvent-depleted coating of the coating forming composition to provide a corrosion resistant and / or abrasion resistant coating on the metal surface.

[014] Curable coating forming compositions of the invention have excellent storage stability and cured surface protective coatings obtained from them tend to exhibit one or more functionally advantageous properties such as high levels of corrosion and abrasion resistance, adhesion to metal surfaces, flexibility (resistance to cracking or cracking caused by bending the metal) and resistance to acid and / or alkaline. In addition, the generally excellent optical clarity of the coatings cured here allows the aesthetically attractive quality of the underlying substrate surface to show a good effect.

DETAILED DESCRIPTION OF THE INVENTION

[015] In the specification and claims here, the following terms and expression should be understood as having the meanings indicated below.

[016] The singular forms "one", "one" and "o / a" include the plural, and reference to a particular numerical value includes at least that particular value unless the context clearly dictates otherwise.

[017] Except in the working examples or where otherwise indicated, all numbers expressing material quantities, reaction conditions, time durations, quantified material properties, and so on, defined in the specification and claims must be understood to be modified in all cases by the term "about".

[018] All methods described here may be performed in any appropriate order unless otherwise indicated here or otherwise clearly contradicted by the context. The use of any and all examples or exemplary language (for example, "such as") provided herein is intended merely to further clarify the invention and does not impose a limitation on the scope of the invention unless otherwise stated.

[019] No language in the specification should be interpreted as indicating any element not claimed as essential to the practice of the invention.

[020] As used here, the terms "comprising", "including", "containing", "characterized by" and grammatical equivalents thereof are inclusive or open terms that do not exclude additional non-recited elements or steps in the method, but will also be understood to include the more restrictive terms "consisting of" and "consisting essentially of".

[021] The percentages of the composition are given in weight percent unless otherwise indicated.

[022] It will be understood that any numerical range recited here includes all sub-ranges within that range and any combination of the various endpoints of such ranges or sub-ranges.

[023] It will be further understood that any compound, material or substance that is expressly or implicitly disclosed in the specification and / or recited in a claim as belonging to a group of structurally, compositionally and / or functionally related compounds, materials or substances includes individual representatives of the group and all combinations thereof.

[024] The term "coating formation composition" is to be understood as meaning a composition, although it is not in itself a practical or useful coating composition, after processing as described here in detail it forms a curable surface protective coating of high quality and thermally effective for application to a metal surface.

[025] The term "metal" as used herein should be understood here as applied to metals per se, metal alloys, metallized parts and metal or metallized parts having one or more non-metallic protective layers.

[026] By "hydrolytically condensed" is meant that one or more silanes in the coating composition forming mixture are hydrolyzed first followed by the condensation reaction of the hydrolyzed product with itself or with other hydrolyzed and / or non-hydrolyzed components of the mixture .

A. COMPONENTS OF THE TRAINING COMPOSITION OF ALCOXISILAN COATING (I)

[027] The alkoxysilane (i) present in the coating formation composition can be one or more dialkoxysilane, trialcoxysilane and / or tetraalkoxysilane of Formula A and / or one or more trialcoxysilane of Formula B as described above provided that at least one such trialcoxysilane is included in it.

[028] Examples of Formula A dialkoxysilanes include dimethyldimethoxysilane, diethyldiethoxysilane, diethyldimethoxysilane, 3-cyanopropylphenyldimethoxysilane, diphenyldimethoxysilane, Diphenyldiethoxysilane, di (p-tolyl) dimethoxysilane, bis (diethylamino) dimethoxy

bis (hexamethyleneamino) dimethoxysilane, Bis (trimethylsilylmethyl) dimethoxysilane, vinylphenyldiethoxysilane and the like and mixtures thereof.

[029] As explained above, alkoxysilanes, including dialkoxysilanes, also include products of the same (oligomers) hydrolyzed and condensed.

[030] Examples of trialkoxysilanes of Formula A include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, etiltripropoxissilano, n-propyltrimethoxysilane, n-propyltriethoxysilane, n propiltripropoxissilano, n-propiltributoxissilano, n-butiltrimetoxissilano, isobutiltrimetoxissilano, n-pentiltrimetoxissilano, n-hexiltrimetoxissilano, isoocyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, octyltrimethoxysilane, trifluoropropyltrimethoxysilane, 3-mercaptopropyltrimethoxyethyl, 3-mercaptopropyltrimethoxyl, 3-mercaptopropyltrimethoxy, 3-mercapto-3-mercapto Of these, methyltrimethoxysilane, octyltrimethoxysilane and glycidoxypropyltrimethoxysilane are especially advantageous.

[031] As explained above, alkoxysilanes, including trialkoxysilanes, also include products of the same (oligomers) hydrolyzed and condensed.

[032] Examples of tetraalkoxysilanes (i.e., tetraalkyl orthosilicates) of Formula A include tetramethoxysilane, dimethoxydiethoxysilane, tetraethoxysilane, methoxytriethoxysilane, tetrapropoxysilane, and the like, and mixtures thereof.

[033] Examples of Formula B trialkoxysilanes include 1,2-bis (trimethoxysilyl) ethane, 1,2-bis (triethoxysilyl) ethane, bis (trimethoxysilylpropyl) disulfide, bis (triethoxysilylpropyl) disulfide, bis (trimethoxysilylpropyl) tetrasulfide, bis ( triethoxysilylpropyl) tetrasulfide, bis (3-triethoxysilylpropyl) amine, bis (3-trimethoxysilylpropyl) amine, and the like, and mixtures thereof.

METAL (II) OXIDE

[034] The metal oxide component (ii) is generally provided in the form of particles, for example, approximately spherical or equiaxial particles, varying in average particle size from about 5 nm to about 500 nm, more specifically from about 10 to about 200 nm and even more specifically from about 10 to about 60 nm. The average particle sizes are determined in particular by Low Angle Laser Light Scattering (LALLS) using Mie's complete theory, in particular, using Mastersizer 2000 or 3000, Malvern Instruments.

[035] Metal oxide (ii) is advantageously provided as an aqueous colloidal dispersion thereof, for example, an aqueous colloidal dispersion of a metal oxide such as silica, alumina, titania, ceria, tin oxide, zirconia, oxide of antimony, indium oxide, iron oxide, titania doped with iron oxide and / or zirconia, rare earth oxide, as well as mixtures and complex oxides thereof. Alternatively, metal oxides (ii) in powder form can be dispersed within the coating composition.

[036] A preferred metal oxide (ii) is aqueous colloidal silica. Aqueous dispersions of colloidal silica that can be advantageously used in the present invention include those having an average particle size ranging from about 20 to about 150 nm and preferably from about 5 to about 30 nm.

Such dispersions are known in the art, of which those commercially available include, for example, Ludox® (Sigma Aldrich), Snowtex® (Nissan Chemical), and Bindzil® (AkzoNobel) and Nalco® Colloidal silica (Nalco Chemical Company), Levasil® (AkzoNobel). Such dispersions are available in the form of acidic and basic hydrosols.

[037] Both acidic and basic colloidal silica can be incorporated into the coating formation composition of the present invention. Colloidal silicas having a low alkali content can provide a more suitable coating composition and can therefore be preferred. Particularly preferred colloidal silicas include Nalco® 1034A (Nalco Chemical Company) and Snowtex® O40, Snowtex ST-033 and Snowtex® OL-40 (Nissan Chemical), Ludox® AS40 and Ludox® HS 40 (Sigma-Aldrich), Levasil 200 / 30 and Levasil® 200 S / 30 (now Levasil CS30-516P) (AkzoNobel) and Cab-O-Sperse® A205 (Cabot Corporation).

[038] If the metal oxide (ii) is as defined in paragraphs [0025] the

[0028], the total amount of alkoxysilane of Formulas A and B preferably does not exceed about 40 weight percent of the coating formation composition.

[039] In one embodiment of the coating formation composition according to the invention, metal oxide (ii) is selected from a mixture of alumina and silica. Preferably for said mixture, the weight ratio of alumina to silica (Al2O3 / SiO2) is from about 1:99 to about 99: 1, preferably from about 5:95 to about 90:10, more preferably about from 5:95 to about 75:25. Such mixtures are preferably prepared by mixing aqueous colloidal dispersions of alumina and silica. Using a mixture of alumina and silica provides good adhesion to the aluminum surface, very high abrasion resistance, good corrosion protection, heat resistance and acid and alkali resistance.

[040] In one embodiment of the coating formation composition according to the invention, metal oxide (ii) is selected from silica modified with alumina. In one embodiment, such alumina-modified silica can be silica, the surface of which has been modified with alumina. Consequently, such alumina-modified silica is sometimes referred to as Al2O3-SiO2 - core-shell particles. Likewise, in this embodiment, the metal oxide (ii) can be advantageously provided as an aqueous colloidal dispersion. The use of such silica modified with alumina or Al2O3-SiO2 - core-shell particles is particularly useful for protecting anodized aluminum components outside automobiles, for example, roof rails and finishing parts and provides high resistance to corrosion caused for liquids with high or low pH, high scratch resistance and high heat resistance. The use of such alumina modified silica in the coating formation composition according to the invention provides high scratch resistance under long-term highly acidic ambient conditions. Examples of alumina modified silica include, for example, Levasil types such as Levasil® 100S / 45 (now: Levasil CS45-58P) dispersion (45% in water) containing Al2O3 surface-modified silica particles having an average particle size about 30 nm, and Levasil® 200S / 30 (now: Levasil CS30-516P) dispersion (30% in water) containing Al2O3-modified silica particles on the surface having an average particle size of about 17 nm, and a surface area of about 85 m² / g (in Levasil® 100S / 45) and about 160 m² / g (Levasil® 200S / 30).

[041] In a particular embodiment using alumina modified silica, a mixture comprising at least two alumina modified silicas having different average particle sizes can be used. For example, a mixture of two alumina modified silicas having different average particle sizes can be used where the weight ratio of alumina modified silica having the smallest particle size (eg 10 to 25 nm) is greater than the amount of the alumina-modified silica having the largest particle size (e.g. 26 to 40 nm), preferably the small / large ratio is about 10: 1 to about 1: 2, preferably about 10: 1 to about 2 :1. This measure provides particularly high risk resistance.

[042] The amount of metal oxide (s) (ii) incorporated in the coating formation composition here can vary, in general, from about 5 to about 50, more specifically from about 10 to about 40 and still more specifically from about 10 to about 30 weight percent based on the weight of the composition.

MISCIBLE SOLVENT IN ORGANIC WATER (III)

[043] Illustrative of water-miscible solvent (s) (iii) that can be incorporated into the coating composition of the invention are alcohols such as methanol, ethanol, propanol, isopropanol, n-butanol, tert-butanol,

methoxypropanol, ethylene glycol, diethylene glycol butyl ether, and combinations thereof. Other water-miscible organic solvents such as acetone, methyl ethyl ketone, ethylene glycol monopropyl ether and 2-butoxy ethanol can also be used. Typically, these solvents are used in combination with water, the latter together with any water associated with metal oxide (ii) and / or other component (s) of the coating composition providing part or all of the water (v) thereof.

[044] The total amount of water-miscible solvent (s) (iii) present in the coating formation composition can vary widely, for example, from about 10 to about 80, more specifically from about 10 to about 65 , more specifically from about 10 to about 60 and even more specifically from about 10 to about 50, weight percent based on their total weight. When the coating composition comprises alumina-modified metal oxide (ii) silica, the total amount of water-miscible solvent (s) (iii) present in the coating composition can vary widely, for example, from about 40 to about 70, more specifically about 50 to about 65 weight percent based on their total weight.

ACID HYDROLYSIS CATALYST (IV)

[045] Any of the acid hydrolysis catalysts used so far for the hydrolysis of alkoxysilanes can be incorporated into the coating composition here. Illustrative acid hydrolysis (iv) catalysts include sulfuric acid, hydrochloric acid, acetic acid, propanoic acid, 2-methyl propanoic acid, butanoic acid, pentanoic acid (valeric acid), hexanoic acid (caproic acid), 2-ethylhexanoic acid, heptanoic acid (enanthic acid), hexanoic acid, octanoic acid (caprylic acid), oleic acid, linoleic acid, cyclohexanecarboxylic acid, cyclohexylacetic acid, cyclohexenecarboxylic acid, benzoic acid, benzenoacetic acid, propanedioic acid (malonic acid) , butanedioic acid (succinic acid), hexanedioic acid (adipic acid), 2-butenedioic acid (maleic acid), lauric acid, stearic acid, myristic acid, palmitic acid, isoanoic acid, versatic acid, lauric acid, stearic acid, myristic acid , palmitic acid, isoanoic acid, amino acids and mixtures thereof. The acid hydrolysis catalyst can be used undiluted or in the form of an aqueous solution.

[046] The acid hydrolysis catalyst (iv) will be present in the coating formation composition of the invention in at least a catalytically effective amount which in most cases can vary from about 0.1 to about 5, more specifically about from 0.5 to about 4.5, and more specifically from about 2 to about 4, weight percent based on the total weight of coating formation composition. In certain embodiments, for example, when the coating composition comprises metal oxide (ii) silica modified with alumina, the amount of the acid hydrolysis catalyst (iv) can also vary from about 0.1 to about 2 weight percent based on the total weight of the coating formation composition.

WATER (V)

[047] The water component of the coating formation composition here is advantageously deionized water (DI). Some or even all of the total water present in the coating composition forming mixture can be added as part of one or more other components of the mixture, for example, aqueous colloidal dispersion of metal oxide (ii), water miscible solvent (iii ), acid hydrolysis catalyst (iv) optional condensation catalyst (vi) and / or other optional components (vii) such as those described below.

[048] The total amount of water (v) can vary within widely varying limits, for example, from about 5 to about 40, more specifically from about 5 to about 30 and even more specifically from about 5 to about 15 percent by weight based on the total weight of the coating formation composition.

OPTIONAL CONDENSATION CATALYST (VI)

[049] The optional condensation catalyst (vi) catalyzes the condensation of partially or completely hydrolyzed components (a) and (b) of the coating formation composition here and thus functions as a curing catalyst.

[050] Although the coating formation composition can be cured in the absence of an optional condensation catalyst (vi), efficient curing may require more intense conditions, for example, the application of high temperature (thermal curing) and / or curing times both of which may be undesirable from a cost and / or productivity point of view. In addition to providing a more economical coating process, the use of optional condensation catalyst (vi) generally results in improved service life of the coating formation composition.

[051] Illustrative of condensation catalysts (vi) that may optionally be present in the coating formation composition here are tetrabutylammonium carboxylates of the formula [(C4H9) 4N] + [OC (O) -R5] - in which R5 is selected from group consisting of hydrogen, alkyl groups containing from 1 to about 8 carbon atoms, and aromatic groups containing from 6 to about 20 carbon atoms. In preferred embodiments, R5 is a group containing about 1 to 4 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl or isobutyl. Compared to more active types of condensation catalysts (v), for example, mineral acids and alkali metal hydroxides, the previous tetrabutylammonium carboxylates, being somewhat lighter in their catalytic action, tend to optimize the useful purpose of coating formation compositions containing them. Exemplary tetrabutylammonium carboxylate condensation catalysts of the previous formula are tetra-n-butylammonium acetate (TBAA), tetrabutylammonium formate, tetra-n-butylammonium benzoate, tetra-n-butylammonium-2-ethylhexanoate, tetra-n-butylammonium-p-ethylbenzoate and tetra-n-butylammonium propionate. In terms of efficacy and suitability for the present invention, preferred condensation catalysts are tetrabutylammonium carboxylate, tetra-n-butylammonium acetate (TBAA), tetra-n-butylammonium formate, tetra-n-butylammonium benzoate, tetra-n-butylammonium- 2-ethylhexanoate, tetra-n-butylammonium-p-ethylbenzoate and tetra-n-butylammonium propionate, tetramethylammonium acetate, tetramethylammonium benzoate, tetrahexylammonium acetate, dimethylanyl formate, dimethylammonate acetate, tetramethylammonium tetramethylammonium tetramethylammonium tetramethylammonium , tetraisopropylammonium acetate, triethanol-methylammonium acetate, diethanoldimethylammonium acetate, monoethanoltrimethylammonium acetate, ethyltriphenylphosphonium acetate, TBD acetate (1,5,7-Triazabicyclo [4.4.0] dec-5-ene (TBD)), as well as combinations of two or more of the same.

[052] Of the previous tetrabutylammonium carboxylate condensation catalysts, tetra-n-butylammonium acetate and tetra-n-butylammonium formate are generally preferred with tetra-n-butylammonium acetate being more preferred.

[053] Where used, the condensation catalyst (vi) can be present in the coating formation composition here in at least a catalytically effective amount, for example, from about 0.0001 to about 1 weight percent based their total weight.

OTHER OPTIONAL COMPONENTS (VII)

[054] One or more other optional components (vii) are suitable for inclusion in the coating formation composition here.

[055] For example, the coating formation composition may also include one or more surfactants acting as leveling agents or flow additives. Examples of suitable surfactants include fluorinated surfactants such as Fluorad® (3M), silicone polyethers such as Silwet® and CoatOSil® (Momentive Performance Materials, Inc.) and silicone surface additives such as modified polyether silicones, such as BYK- 302 (BYK Chemie USA). The coating composition herein may also include a UV absorber such as benzotriazole, benzophenones,

dibenzylresorcinol. Preferred UV absorbers are those capable of co-condensing with silanes, the specific examples of which include 4- [gamma- (trimethoxysilyl) propoxyl] -2-hydroxy benzophenone, 4- [gamma- (triethoxysilyl) propoxyl] -2-hydroxy benzophenone and 4,6-dibenzoyl-2- (3-triethoxysilylpropyl) resorcinol. When preferred UV absorbers that are capable of co-condensing with silanes are used, it is important that the UV absorber co-condenses with other reaction species by thoroughly mixing the thermally curable coating composition here before applying it to the surface of a metal. The co-condensation of the UV absorber prevents the loss of performance of the coating that can be caused by the leaching of free UV absorbers into the environment during weathering.

[056] The coating formation composition here may also include one or more antioxidants such as a hindered phenol (for example, Irganox® 1010 (Ciba Specialty Chemicals), dyes such as methylene green, methylene blue and the like), fillers such as titanium dioxide, zinc phosphate, barites, aluminum flakes, etc. and plasticizer such as dibutyl phthalate. B. FORMATION OF THE COATING FORMATION COMPOSITION.

[057] In forming the thermally curable coating composition of the invention, cooling a mixture of alkoxysilane (s) (i) and a portion of the acid hydrolysis catalyst (iv), subsequent addition of the remaining portion of acid hydrolysis catalyst (iv) ) and aging of the resulting mixture under predetermined conditions of temperature and elevated time leads to a thermally curable composition having a viscosity range of about 3.0 to about 7.0 cStks, in another embodiment more specifically about 4.0 at about 5.5 cStks and in yet another embodiment more specifically from about 4.5 to about 5.0 cStks.

[058] Cooling can be done, for example, by using an ice bath, ice / NaCl mixture or dry ice / isopropanol mixture. More specifically, the alkoxysilanes (i) and the acid hydrolysis catalyst (iv) are placed in a glass bottle and then placed in an ice bath to cool the mixture while monitoring the temperature using an external thermometer. Cooling of the mixture of alkoxysilanes (i) and the acid hydrolysis catalyst (iv) is preferably done to a temperature of about -20oC to about 15oC, preferably of about -10oC to about 10oC, more preferably about from 0 to about 10 ° C.

[059] In a first stage of the process of forming the thermally curable coating composition here, a mixture of Formula A and / or B trialcoxysilane, optional dialcoxysilane and / or Formula A tetra-alkoxysilane and about 10 to about 40 percent of the total amount of acid hydrolysis catalyst (iv) is cooled to within a temperature range of about -20oC to about 15oC, and preferably about -10oC to about 10oC.

Although in the cooled condition, metal oxide (ii), for example, aqueous colloidal silica, is slowly added to the mixture.

[060] After adding metal oxide (ii) and with constant stirring for a period of about 2 to about 10, and more specifically about 5 to about 8 days, the cooled mixture is allowed to rise in temperature up to or about ambient, for example, from about 20oC to about 30oC. During this period of continuous stirring, the alkoxysilane component (s) of the mixture undergoes an initial level of hydrolysis followed by condensation of the resulting hydrolysates.

[061] When metal oxide (ii) is selected from silica modified with alumina, it is preferred to cool these formulations for a few hours / overnight, for example, for about 2 to about 10 hours.

[062] In a second stage of the process for forming the thermally curable coating composition here, water-miscible solvent (s) (iii) and the remaining acid hydrolysis catalyst (iv) are now added to the reaction medium at room temperature and under continuous agitation for a period of, for example, from about 5 to about 24, and more specifically from about 8 to about 15, hours during which additional hydrolysis of silanes and / or partial hydrolysates and condensation of the so hydrolyzed formed from them occurs.

[063] When metal oxide (ii) is selected from silica modified with alumina, it is preferred to add the entire amount of the acid hydrolysis catalyst (iv) directly at the beginning, so there is no addition of the acid hydrolysis catalyst (iv) in this Score.

[064] The addition of part of the acid hydrolysis catalyst (iv) in the first stage and the addition of the remaining acid hydrolysis catalyst (iv) in the second stage results in a curable coating composition within the viscosity range mentioned above. The rates of hydrolysis and condensation reaction are dependent on the concentration of acid hydrolysis catalyst (iv) and the pH of the reaction mixture. The final pH of the reaction mixture is advantageously maintained from about 2 to about 7, and more specifically from about 4 to about 6. The acid hydrolysis catalyst (iv) is added in two stages in order to maintain the pH at each stage. The initial portion of acid hydrolysis catalyst (iv) is added in such a way, for example, in drops, to prevent the agglomeration and precipitation of metal oxide particulate (ii) thereby allowing the alkoxysilane component (s) (i ) undergo hydrolysis and functionalize the metal oxide particles (ii). With the silanization of metal oxide particulates (ii), the pH of the mixture will become almost neutral.

[065] When metal oxide (ii) is selected from silica modified with alumina, usually pH ranges of about 3 to about 4 such as about 3.5 to about 3.8 are achieved with no adjustment of additional pH.

[066] The acid hydrolysis catalyst (iv) can be added in the second stage to maintain the final pH of the mixture so that the condensation of silanol is controlled and gel formation is inhibited, thereby providing relatively long life, for example, a coating formation composition containing less than about 5, preferably less than about 2 and more preferably less than about 1, gel weight percent of their total weight after storage at room temperature of not less than about 15 days, more specifically not less than about 20 days and even more specifically not less than about 30 days. In certain embodiments, storage at temperatures in the range of about 0 to about 15 ° C, preferably about 5 to about 10 ° C, may be appropriate.

[067] If used, optional condensation catalyst (vi) can be added in at least a catalytically effective amount in, during or after any of the steps (a) - (d) of preparing the curable coating composition. The amounts of optional condensation catalyst (v) can vary widely, for example, from about 0.01 to about 0.5, and more specifically from about 0.05 to about 0.2, weight percent based on the total weight of coating formation composition.

[068] The optimum amount of residual silanol is obtained by accelerating the condensation reaction during aging as described more fully below. Once the desired viscosity level is achieved, the curable coating composition can be applied to a desired substrate to produce a uniform, transparent and hard coating on it (steel wool abrasion resistance test with 1 kg load as described) in Table 5 below.

[069] After this hydrolysis period, optional condensation catalyst (v) and one or more other optional components (vii) can be added to the reaction mixture, advantageously under continuous stirring for an additional period of time, for example, by about 1 to about 24 hours. The resulting reaction mixture is now ready for aging.

[070] The aging of the previous coating composition formation mixture is carried out at an elevated temperature for a period of time that has been experimentally determined to result in a viscosity within the mentioned range before about 3.0 to about 7.0 cStks.

[071] When metal oxide (ii) is selected from silica modified with alumina, aging is normally not required.

[072] Obtaining such viscosity results in a curable coating composition with good to excellent cured coating properties. Lower viscosity can lead to reduced hardness of the coating film and post-curing that can occur through continuous exposure of the coating. Higher viscosity can lead to cracking of the coating film during curing conditions and subsequent exposure.

[073] For many coating composition forming mixtures, a viscosity within the range of about 3.0 to about 7.0 cStks can be achieved by heating the coating forming mixture in an air oven, for example , up to a temperature of about 25 to about 100 oC for about 30 min. at about 1 day, more specifically at a temperature of about 25 to about 75 oC for about 30 min to about 5 days and even more specifically at a temperature of about 25 to about 50 oC for about 3 about 10 days. The hydroxyl-containing hydrolyzable silane is partially hydrolyzed when less than an equivalent amount of water reacts with the hydrolyzable silyl group. Silane is considered partially hydrolyzed when centoual hydrolysis is in the range of about 1 to about 94 percent. Hydrolyzable silane containing hydroxyl is considered substantial and fully hydrolyzed when the percent hydrolysis is in the range of about 95 to about 100 percent. The hydrolyzable silane containing partially hydrolyzed hydroxyl has better stability in an aqueous solution because the R1O-Si group terminates the silanol condensation polymerization reaction and maintains an oligomeric composition with a lower average molecular weight that is derived from the hydrolyzable silane containing hydroxyl. The oligomeric composition with lower average molecular weight adsorbs more evenly on the metal substrate resulting in better adhesion.

C. APPLICATION OF COATING AND HEALING PROCEDURES

[074] The coating formation composition of the invention, with or without the other addition of added solvent (s), will typically have a solids content of about 10 to about 50, more specifically about 15 to about 40 and even more specifically from about 20 to about 30 weight percent. The pH of the coating composition will often be within the range of about 3 to about 7, and more specifically about 4 to about 6.

[075] When metal oxide (ii) is selected from silica modified with alumina, the pH of the coating composition will often be within the range of about 3 to about 4 such as about 3.5 to about 3 , 8.

[076] The curable coating composition can be coated on a metal substrate with or without the use of a primer and preferably without a primer.

[077] Suitable metals include steel, stainless steel, aluminum, anodized aluminum, magnesium, copper, bronze, alloys of each of these metals, and the like, with anodized aluminum being a particularly desirable substrate due to its corrosion resistance property inherent strength and resistance to weight ratio.

[078] The coating formation composition can be applied to a metal surface or other substrate employing any known conventional technique or otherwise such as spray coating, scrubbing and flow. Likewise, dip coating is possible. The thickness of the wet coating, i.e., freshly applied, can be made to vary over a reasonably wide range, for example, from about 10 to about 150, more specifically from about 20 to about 100, and even more specifically about 40 to about 80 microns. As applied coatings of such thicknesses upon drying will generally provide cured coatings having thicknesses ranging from about 3 to 30, more specifically from about 5 to about 20, and even more specifically, from about 10 to about 15 microns respectively.

[079] When metal oxide (ii) is selected from alumina modified silica, typically dry coating thicknesses (DFT) of about 2 to about 10 microns, preferably about 3 to about 7 microns are adjusted.

[080] As the coating dries, the solvent (s) (iii) and any other readily volatile material (s) will evaporate and within a short time, for example, 15-30 minutes or so, the coating applied will become free of adhesion to the touch to which the coating / film layer can be considered ready for curing advantageously employing conventional or otherwise known thermal curing procedures, whose operational requirements are well known in the art. For example, thermally accelerated curing can be performed within a temperature range of about 80 to about 200 oC for a period of about 30 to about 90 minutes to provide a hard, optically transparent, cured protective coating on the metal substrate.

[081] The cured coating obtained from the coating forming composition of the invention can be in direct contact with the metal surface, can serve as the unique coating on it, can be superimposed by one or more other coatings and / or can have itself only one or more other coatings superimposed on it. The cured coating composition, in addition to imparting corrosion and / or abrasion resistance properties to your metal substrate, can also function as an aesthetic coating in which case it will constitute the single or most external coating on the metal substrate.

[082] The advantages of the coating composition of the invention over the known alkoxy silane based coating compositions lie not only in the exceptional storage stability of the first, attributable, it is believed the particular combination of starting components and their quantities and for the unique process by which the coating formation composition is obtained, in particular, its separate cooling, split addition of hydrolysis catalyst and aging steps, but in the ease of its application to any of a variety of surfaces metal and metallized and the reasonably uniform properties of the cured coating.

[083] As indicated earlier, the cured coating composition of the invention exhibits excellent properties including a high level of adhesion to its metal substrate, corrosion resistance, flexibility (crack and crack resistance), abrasion / wear resistance and optical clarity , the latter being a particularly sought after property where the cured coating composition is to function additionally as a decorative coating.

EXAMPLES COMPARATIVE EXAMPLE 1

[084] Comparative Example 1 illustrates a curable coating formation composition prepared according to Burger et al. U.S. Patent No.

6,695,904 and applied to an anodized aluminum panel 15 cm long, 4 cm wide and 4 mm thick.

[085] A mixture of methyltrimethoxysilane, 62.0 g, tetraethoxysilane, 18.1 g and aqueous colloidal silica, 23.13 g (40% by weight of suspension) was prepared which was added in drops at -5oC 1.3 g of 37 weight percent sulfuric acid as a catalyst for acid hydrolysis. A mixture was stirred continuously at 20 ° C for one hour to provide a coating composition. Within a few hours, the reaction mixture gelled. However, after 1 hour, an attempt was made to flow-coat the mixture on an anodized aluminum substrate at 23 oC and 40% RH to a uniform thickness of about 10-15 microns. After the flow coating, volatiles were allowed to evaporate for a wash time of 25 minutes, the coating was cured at 130 oC for 1 hour.

[086] The resulting cured coating was opaque, exhibited widespread cracking and had delaminated indicating little if there was any adhesion to the underlying anodized aluminum surface.

[087] A sample of the coating composition aged at 50oC for 24 hours had completely gelled and a sample of the coating composition kept at around 23oC had completely gelled within 24 to 48 hours. Due to its instability, the viscosity of the coating composition cannot be measured.

EXAMPLES 1-15 (COLOIDAL SILICON USING METAL (II) OXIDE)

[088] Examples 1-15 illustrate the preparation of coating compositions of the invention and their performance as cured coatings on anodized aluminum panels 15 cm long, 4 cm wide and 4 mm thick and on steel panels stainless steel 15 cm long, 10 cm wide and 1 mm thick.

[089] The starting components of the curable coating forming compositions of Examples 1-15 are listed in Table 1 below: TABLE 1: RAW MATERIALS Component Chemical name 1a methyltrimethoxy silane 1b glycidoxypropyltrimethoxy silane 1c glycidoxypropyl-trimethoxysilane oligomeric Trialcoxysilane 1d bis ( triethoxysilylpropyl) tetrasulfide 1e trifluoropropyltrimethoxysilane 1f bis (triethoxysilylpropyl) disulfet tetraethoxysilan 2 tetraethoxysilane (ie the optional tetraethylorthosyllate)

3rd acetic acid hydrolysis catalyst Catalyst 3b tetrabutyl ammonium acetate condensation catalyst (TBBA) metal oxide 4a aqueous colloidal silica, 40 weight percent solids water 5 deionized water solvent 6 2-propanol 7 n-butanol additive 8 flow additive BYK-302 (1% methoxypropanol surface) silicone

[090] The general procedure used for forming the curable coating forming compositions of Examples 1-15 is described below in Table 2: TABLE 2: PREPARATIVE PROCEDURE Step Description 1 A glass container was loaded with part of the hydrolysis catalyst from acetic acid and all trialkoxysilane (s). 2 After cooling the Step 1 mixture in an ice bath to 0 ° C, a mixture of aqueous colloidal silica and water was added in drops to it while maintaining the temperature below 10 ° C. The mixture was then stirred for approximately 16 hours during which time the temperature of the mixture rose to room temperature. 3 The remaining alcohols and acetic acid hydrolysis catalyst were then added and the mixture stirred for approximately 12 hours after the addition of TBAA condensation catalyst and flow additive. 4 The mixture from Step 3 was aged for approximately 6 days at 50oC in a hot air oven. The viscosity of each curable coating composition was measured and determined to be within the range of about 3.0 to about 7.0 cStks.

[091] Using the raw materials listed in Table 1 and the general preparatory procedure described in Table 2, the curable coating formation compositions of Examples 1-15 were prepared from the indicated mixtures shown in Table 3 below: TABLE 3: COATING TRAINING COMPOSITIONS

CURABLE Component Example (from Table 1) Percent by weight 1a 35.44 3a 2.73 3b 0.104 4a 14.6 example 1 5 12.6 6 16.63 7 16.42 8 1.82 1a 33.77 2 1 , 69 3a 2.73 3b 0.105 Example 2 4a 14.27 5 12.62 6 16.63 7 16.42 8 1.82 1a 32.22 2 3.23 3a 2.73 3b 0.104 Example 3 4a 14.26 5 12.71 6 16.63 7 16.42 8 1.82 1a 30.82 2 4.62 Example 4 3a 2.73 3b 0.104

Component Example (from Table 1) Percent by weight 4a 14.27 5 12.6 6 16.63 7 16.42 8 0.104

1a 29.53 2 5.91 3a 2.73 3b 0.104 Example 5 4a 14.26 5 12.6 6 16.63 7 16.42 8 0.104

1a 33.75 1d 1.69 3a 2.74 3b 0.104 Example 6 4a 14.26 5 12.61 6 16.63 7 16.43 8 1.82

1a 32.24 1d 3.22 3a 2.73 3b 0.105 Example 7 4a 14.26 5 12.6 6 16.64 7 16.42 8 1.82

1a 29.53 1d 5.91 3a 2.73 Example 8 3b 0.104 4a 14.26 5 12.6

Component Example (from Table 1) Percent by weight 6 16.63 7 16.42 8 1,, 82

1a 33.75 1f 1.69 3a 2.73 3b 0.105 Example 9 4a 14.29 5 12.6 6 16.63 7 16.42 8 1.82

1a 32.22 1f 3.22 3a 2.73 3b 0.104 Example 4a 14.26 10 5 12.61 6 16.63 7 16.42 8 1.82

1a 29.53 1f 5.91 3a 2.73 3b 0.104 Example 4a 14.26 11 5 12.6 6 16.63 7 16.42 8 1.82

1a 33.79 1e 1.7 3a 2.74 Example 3b 0.105 12 4a 14.28 5 12.63 6 16.64 7 16.4

Component Example (from Table 1) Percent by weight 8 1.82 1a 32.27 1e 3.24 3a 2.77 3b 0.105 Example 4a 14.29 13 5 12.63 6 16.65 7 16.43 8 1, 82 1a 33.41 1b 1.67 3a 2.7 3b 0.103 Example 4a 14.11 14 5 12.47 6 16,, 46 7 16.25 8 1.8 9 2.81 1a 33.75 1c 1.69 3a 2.73 3b 0.104 Example 4a 14.26 15 5 12.6 6 16.63 7 16.42 8 1.82

[092] The viscosities of the coating forming compositions of Example 1, 3 and 15, shown in Table 4 below, were measured according to DIN 53015, "Viscometry - Measurement of Viscosity by Means of the Rolling Ball Viscometer by Hoeppler "at 25 oC using a Model 356-001 Hoeppler ball drop viscometer equipped with a Haake DC10 temperature control unit and set of balls 800-0182, in particular ball # 2 having a diameter of 15,598 mm, a weight of 4,4282 g and a density of 2,229 g / cm3. TABLE 4: VISCOSITIES OF TRAINING COMPOSITIONS

CURABLE COATING Example Viscosity, cStks 1 4.9936 3 4.8850 15 4.8678

[093] The general procedures for applying the curable coating forming compositions of Examples 1-15 to anodized aluminum and stainless steel panels and curing the coatings on them as follows:

COATING PROCEDURE

[094] The application of a coating layer having an approximate thickness of 10 microns can be carried out by any suitable means, for example, by dip, flow or spray coating. The dip coating was used to apply a layer approximately 10 microns thick of the coating formation composition to the anodized aluminum panels while flow coating was used to apply a coating of this thickness to the stainless steel panels.

HEALING PROCEDURE

[095] After applying coatings to anodized aluminum and stainless steel substrates, volatiles were evaporated at about 23 oC resulting in the formation of adhesion-free coating layers within about 25 minutes. The coated panels were then baked in a hot air oven at 130oC for 45-60 minutes to produce a hard, transparent coating, completely cured on the metal surfaces.

[096] The test of the coated metal panels was performed as described below in Table 5: TABLE 5: TESTING OF COATED PANELS Test Procedure Appearance of one The appearance of the panels was by inspection

Test Procedure visual panel.

To pass the appearance test, a coating had to be smooth, shiny, optically transparent and free of other visible defects.

Adhesion of the The adhesion test was performed according to the coating with ASTM D 3359 (5B considered panel as the best adhesion, 0B considered as no adhesion) Resistance to The scratch / abrasion scratch / abrasion resistance test was performed using steel wool grade 0000 coating, taped to the end of a 1x1 inch bar, weighing 1 kg.

The steel wool side was wiped back and forth 10 times over the lining followed by visual inspection of the lining for scratches.

A coated panel was considered to have passed this test if there were no visible risks.

Resistance to The coated panels were kept in a hot air oven at 160 oC for 24 hours.

To pass this test, there was no observable loss of adhesion, delamination or cracking.

Resistance to The coated panels were immersed in alkaline acids in a solution of phosphate buffer pH 1.0 HCI / pH 13.5 for 10 minutes.

The panels were then removed from the buffer solution, washed with DI water and dried at room temperature (approximately 23 oC). To pass this test, there must be no softening of the coating film, loss of adhesion, delamination, cracking or corrosion.

Resistance to This test was performed by DIN EN ISO humidity 6270-2-CH.

To be acceptable, the coating had to pass 240 hours according to this test.

This test was performed by DIN EN ISO resistance to 9227. To be acceptable, the spray coating had to pass 48 hours according to this accelerated salt test. copper (CASS) test This test was performed by DIN EN ISO resistance to 9227. To be acceptable, a

Test Coating spray procedure had to pass 480 hours neutral salt (NSS) according to this test.

[097] The coating performance data are presented in Tables 6-9 as follows: TABLE 6: COVER PERFORMANCE ON

ANODIZED ALUMINUM SUBSTRATES Exe Appearance of Abrasion Adhesion Resistance Resistance mpl initial wool or heat resistance steel to acid alkali 1 Transparent / Passed 5B Step Passed Step Passed Smooth / Glossy uu 2 Transparent / Passed 5B Step Passed Step Passed Smooth / Bright uu 3 Transparent / Passed 5B Step Passed Step Passed Smooth / Bright uu 4 Transparent / Passed 5B Step Passed Step Passed Smooth / Bright uu 5 Transparent / Passed 5B Step Passed Step Passed Smooth / Bright uu 6 Transparent / Passed 5B Step Passed Step Passed Smooth / Bright uu 7 Transparent / Passed 5B Step Passed Step Passed Smooth / Bright uu 8 Transparent / Passed 5B Step Passed Step Passed Smooth / Bright uu 9 Transparent / Passed 5B Step Passed Step Passed Smooth / Bright uu 10 Transparent / Passed 5B Step Passed Step Passed Smooth / Glossy uu 11 Transparent / Passed 5B Step Passed Step Passed Smooth / Glossy uu 12 Transparent / Passed 5B Step Passed Step Passed Smooth / Bright uu 13 Transparent / Passed 5B Step Passed Passed Smooth / Bright uu 14 Transparent / Passed 5B Step Passed Passed Smooth / Bright uu 15 Transparent / Passed 5B Step Passed Step Passed Smooth / Bright uu TABLE 7: FINISHING PERFORMANCE ABOUT SUBSTRATE

OF POLISHED BULK ALUMINUM

Example Appearance of the coating Adhesion Abrasion Resistance to the initial heat wool steel 1 Transparent / Smooth / Glossy Passed 5B Passed 10 Transparent / Smooth / Glossy Passed 5B Passed PASSED TABLE 8: PERFORMANCE OF STAINLESS STEEL COATING

SUBSTRATE Abr asã Appearance of the Adhesion Ex cia wool in initial heat resistance coating Transparent steel / Smooth / Br Step Pas 1 ilhante u 5B sou Passed TABLE 9: CORROSION PERFORMANCE ON SUBSTRATE OF

ANODIZED ALUMINUM Exe Test Resistance to Resistance CAS mpl humidity, 240 to NSS, 480 S, 48 ohhh 1 Passed Pass Pass or EXAMPLES 16 to 25 (USING A MIXTURE OF SILICA AND ALUMINUM PARTICLES AS METAL (II) OXIDE) TABLE -10: RAW MATERIALS Chemical name Name Tracks (% in commercial / weight in the formulation) Trialcoxis 1a methyltrimethoxy silane A-163 35 silane (MTMS) Catalyzed 3rd hydrolysis catalyst Aldrich 3 or acetic acid 3b TBAA catalyst 0, 10 condensation of tetrabutyl ammonium acetate (TBBA) oxide a SiO2 dispersion LUDOX A 3-14 metal (silica) S40 b Al2O3 dispersion Aldrich 1-22 (alumina)

water 5 DI 13-19 deionized water Solvents 6 2-propanol Aldrich 0-16 7 n-butanol Aldrich 15-17 Additives 8 flow additive BYK- BYK-302 2 302 (1% in methoxypropanol) TABLE-11: EXAMPLES 16 -25 (ALL FIGURES REFER TO% BY WEIGHT BASED ON TOTAL COMPOSITION) Examples Ex Ex- Ex-18 Ex- Ex-20 Ex-21 Ex- Ex Ex Ex - 17 19 22 -23 -24 -25 16 Acid 0.8 0.85 0.85 0.84 0.85 0.85 0.84 0.8 0.8 0.8 acetic 4 5 5 4 MTMS 35, 35.1 35.09 35.0 35.09 35.12 35.0 35, 35, 35, 08 0 8 8 08 07 08 Al2O3 1.4 2.27 2.56 2.82 3.12 3.42 4.24 7.1 14, 21, colloidal 2 3 26 40 SiO2 13, 12.9 12.87 12.7 12.57 12.47 12.0 10, 7.1 3.5 colloidal 41 9 0 1 70 3 7 water DI 13, 13.2 13.40 13.4 13.58 13.65 13.8 14, 16, 19, 02 9 5 6 74 09 02 Iso-15, 14.8 14.62 14.3 14.17 13.97 13.2 10, 5 , 1 0,0 propanol 62 5 7 6 82 2 0 n-Butanol 16, 16.4 16.42 16.4 16.47 16.47 16.4 16, 16, 15, 43 4 2 2 53 53 94 Acid 1.8 1.90 1.89 1.89 1.89 1.89 1.90 1.8 1.8 1.8 acetic 9 9 9 9 BYK 302 1.8 1.82 1.82 1.82 1 , 82 1.82 1.82 1.8 1.8 1.8 (1% in 2 2 2 2 MP) TBAA 0.1 0.10 0.104 0.10 0.104 0.104 0.10 0.1 0.1 0.1 04 4 4 4 05 04 05

COATING FORMULATIONS WERE PREPARED BY ANY PROCEDURE TO FOLLOW: SINGLE STEP PROCEDURE FOR COATING FORMULATIONS:

[098] A glass bottle was loaded with acetic acid and trialoxy silane. After cooling the reaction mixture in an ice bath to 0 ° C, the mixture of silica nanoparticles and water was added in drops to the cooled mixture of silanes and acetic acid while maintaining the temperature below 10 ° C. The mixture was then allowed to stir for approximately 1-2 hours. The alumina nanoparticle dispersion was then added to the mixture, and allowed to stir for approximately another 12-14 hours while the temperature of the solution slowly increased to room temperature. Then, alcohols and remaining acetic acid were added and stirred for approximately 12 hours after which the TBAA catalyst and flow additive were added.

After that, the formulations were aged for approximately 5 days at 50 ° C in a hot air oven before coating on the metal surface.

TWO-STEP PROCEDURE FOR COATING FORMULATIONS:

[099] In this method, coating solutions can be prepared by reacting alkoxy silane with different nanoparticles separately. This method may be a better choice over the one-step procedure for compositions where there is a tendency for nanoparticles to settle in the formulation. However, this method can be used, in general, for coating compositions having any ratios of two different nanoparticles. In this method, a glass bottle was loaded with acetic acid and trialoxy silane. After cooling the reaction mixture in an ice bath to 0 ° C, the mixture of silica nanoparticles and water was added in drops to the cooled mixture of silanes and acetic acid while maintaining the temperature below 10 ° C. The mixture was then allowed to stir for approximately 16 hours while the temperature of the solution slowly rose to room temperature. In another glass bottle, a portion of alkoxy silane (preferably 1: 1 weight percentage of silane and nanoparticle) and nanoparticle (alumina) were mixed together and kept under stirring for approximately 16 h at room temperature. After that, both solutions were mixed together at room temperature and kept under stirring for 1-2 hours. Then, alcohols and remaining acetic acid were added and stirred for approximately 12 hours after which TBAA catalyst and flow additive were added. After that, the formulations were aged for approximately 5 days at 50 ° C in a hot air oven before coating on the metal surface.

GENERAL PROCEDURE FOR METAL SURFACE COATING:

[0100] The coating composition is an optically transparent, single-layer thermal curing protective coating that has been applied directly to anodized aluminum surfaces. The application of a thin layer coating of approximately 10 microns in thickness was achieved by immersion / flow / spray coating. After coating on aluminum substrates, volatiles evaporate at ambient conditions (approximately 20-25 ° C, 40 ± 10% RH) and an adhesion-free coating layer is formed within 25-30 minutes. After solvent washing, the coated panels were baked in a hot air oven at 130-200 ° C for 30-60 minutes to obtain a hard, transparent coating, completely cured on a metal surface.

TEST METHODS (EXAMPLES 16-25):

[0101] Appearance of the coating: This test is done by visual inspection.

To pass, the coating must be smooth, shiny, optically transparent and free from any coating defects.

[0102] Initial adhesion: The Cross Hatch adhesion test is done according to the standard procedure ASTM D 3359. To be acceptable, the entire coating must pass 5B.

[0103] Machine abrasion resistance test for color fastness testing by machine friction for color fastness testing by crockmeter: This test is done by AATCC Crockmeter CM-5 instrument using green cloths with friction fade 5 cm x 5 cm (from Atlas) for 10 cycles (1 cycle = rubbing back and forth); distance: 100 mm; strength: 9 N

(applied automatically). To pass this test, there must be no visible scratches on the surface after the test.

[0104] Heat resistance: The coated panels are kept in a hot air oven at 160 ° C for 24 h. To pass, there should be no loss of adhesion, delamination or cracking.

[0105] Hydrochloric acid resistance test: The coated panels are immersed in a pH 1.0 hydrochloric acid (HCl) solution for 10 minutes. After exposure, the panels are removed from the solution, washed with DI water and dried under ambient conditions. To pass, there must be no softening of the coating film, loss of adhesion, delamination, cracking or corrosion.

[0106] Alkaline resistance test: The coated panels are immersed in a pH 13.5 sodium hydroxide buffer solution for 10 minutes. The buffer solution is prepared by mixing the appropriate weight of sodium hydroxide, sodium phosphate dodecahydrate, sodium chloride and deionized water. After exposure, the panels are removed from the solution, washed with DI water and dried under ambient conditions. To pass, there must be no softening of the coating film, loss of adhesion, delamination, cracking or corrosion.

[0107] Sulfuric acid resistance test: The coated panels are immersed in a solution of H2SO4 pH 2.1 for 5 days. After exposure, the panels are removed from the solution, washed with DI water and dried under ambient conditions. To pass, there must be no softening of the coating film, loss of adhesion, delamination, cracking or corrosion.

[0108] Corrosion resistance test - Kesternich test (acid rain simulation): This test is done according to DIN 50017 up to 3 cycles. To pass this test, the coating must not exhibit any softening, delamination, loss of adhesion, changes in visual appearance or any other defects in the coating.

TABLE 12: TEST RESULTS - EXAMPLES 16-25 Exe Appearance Ade Test Resistance Resistance Resistance Resistance Resistance to Crockm Alkaline acid acid heat pH 1.0 pH 3.5 Test HCl H2SO4 pH 13 .5 NaOH buffer

16 Transpare 5B Pass Pass Pass Pass Pass, No defects

17 Transpare 5B Pass Pass Pass Pass Pass, No defects

18 Transpare 5B Pass Pass Pass Pass Pass, No defects

19 Transpare 5B Pass Pass Pass Pass Pass, No defects

20 Transpare 5B Pass Pass Pass Pass Pass, No defects

21 Transpare 5B Pass Pass Pass Pass Pass, No defects

22 Transpare 5B Pass Pass Pass Pass Pass, No defects

23 Transpare 5B Few Passes Passes Passes Pass, No risk defects

24 Transpare 5B Few Pass Pass Pass Pass, No risk defects

25 Transpare 5B Few Passes Passes Passes Pass, No risk defects

CORROSION RESISTANCE TEST: KESTERNICH TEST (ACID RAIN SIMULATION)

[0109] Examples 19, 23, 24 and 25 were subjected to the Kesternich test and all passed the test.

[0110] As evidenced by these tests, the inventive compositions of examples 16-25, comprising particles of silica and alumina, all provide good coating properties such as adhesion, abrasion and pH resistance tests (HCl and NaOH buffer solution) . In particular, the examples also provide very good results with respect to scratch resistance, pH resistance test including resistance to sulfuric acid and in the Kesternich tests.

EXAMPLES 26 TO 30 (AL2O3-SIO2 - PARTICLES OF THE NUCLEUS TYPE - SHELL LIKE METAL OXIDE (II)) TABLE 13: RAW MATERIALS Component Chemical name 1a methyltrimethoxy silane Trialcoxysilane 1b glycidoxypropyltrimethoxy silane catalyst catalyst 3 catalyst hydrolysis catalyst condensation tetrabutyl ammonium acetate (TBBA) metal oxide 4c Levasil 100S / 45 45 weight percent solids metal oxide 4d Levasil 200S / 30 30 weight percent solids deionized water 5 solvent deionized water 6 isopropanol 7 n- butanol additive 8 flow additive BYK-302 silicone surface (1% in methoxypropanol) TABLE-14: EXAMPLES 26-30

(ALL FIGURES REFER TO% BY WEIGHT BASED ON TOTAL COMPOSITION)

Ex Ex Ex Ex E 26 27 28 29 x 3 0 MT 37, 34.5 33, 26, 1 MS 04 9 90 87 9, 9 6 Glici 0.0 3.84 3.7 13, 1 doxi 0 7 44 0 , prop 0 il- 1 trim ethoxy silica in Lev 7.0 7.33 3.6 4.4 3, asyl 6 0 7 3 100 2 S / 4 5 Lev 9.2 9.60 4.7 14, 1 asyl 6 3 90 2, 200 0 S / 3 3 0 Water 13, 13.8 13, 0.0 0, at 23 3 56 0 0 0 n- 15, 15.7 15, 24, 2 But 18 4 92 43 6, anol 8 7 Isop 15, 15.7 15, 24, 2 ropa 18 4 92 43 6, nol 8 7 Acid 2.8 2.95 2.8 3.4 0, 5 9 2 7 acetic 7 BYK 0.1 0.10 0.1 0.0 0, 302 0 0 5 0 6

TBA 0.1 0.10 0.1 0.1 0, A 0 0 3 1 2

PREPARATION OF COATING COMPOSITIONS

[0111] The mixture of core-shell particles Levasil 100S / 45 and Levasil 200S / 30 and acetic acid is stirred in a flask. The mixture is cooled to 0 - 10 ° C while the silanes are added in drops within 20 - 50 min. The mixture is stirred while the solution is allowed to reach room temperature. The next day, the alcohols, the catalyst and the flow additive are added. The entire mixture is stirred for at least 15 min.

COATING PROCEDURE

[0112] After preparation, the transparent coating compositions were applied directly on anodized aluminum with a layer thickness of 2 µm to 8 µm. The application of the coating compositions was achieved by dip / flow or spray coating. After coating anodized aluminum substrates, the solvent wash takes 2 - 20 min to obtain an adhesion-free coating layer. The coated substrates are then cured in a hot air oven at 130 ° C to 200 ° C for 30 min up to 2 hours to obtain complete curing. TABLE 15: TEST RESULTS - EXAMPLES 26-30

[0113] The following tests and test procedures were performed on anodized aluminum parts.

[0114] The SO2 laboratory test transferred from the DIN50018 - 2.0S solution: 0.67% by weight of SO2 in a 5L bottle that is placed in a water bath at 40 ° C. The coated samples are placed with the bottom in this solution, while the top experiences the SO2 atmosphere. According to the test specification, the coating should not change optically after five days.

[0115] Alkaline resistance according to TL182: No change in appearance after the following series of tests on the same component over a temperature range of 23 ° C to 35 ° C: a) 10 double rubs with 1 kg load b) 10 min immersion in pH 1 solution (0.1 molar hydrochloric acid) c) Rinse in water and dry d) Aging at 40 ° C for 1 h, then the test sequence continues without cooling e) 10 min immersion in pH 13.5 solution (12.7 g of caustic soda, 4.64 g of sodium phosphate dodecahydrate, 0.33 g of sodium chloride; all dissolved in 1 liter of water) 48 h salt spray test according to DIN EN ISO 9227 (CASS test).

[0116] The following table summarizes the results of the different coating compositions: TABLE 15 Example Test Resistance Test Laboratory CASS Test Alkaline SO2 Alkaline 26 ok ok ok Ok 27 ok - - - 28 ok - - - 29 ok ok ok ok 30 ok ok ok ok

[0117] Although the invention has been described above with reference to specific modalities thereof, it is apparent that many changes, modifications and variations can be made without departing from the inventive concept described here. Consequently, it is intended to cover all such changes, modifications and variations that are within the spirit and broad scope of the attached claims.

Claims (34)

1. Coating formation composition, CHARACTERIZED by the fact that it comprises: (i) at least one alkoxysilane selected from the group consisting of Formulas A and B: (X-R1) to Si (R2) b (OR3) 4- ( a + b) Formula A (R3O) 3Si-R1-Si (OR3) 3 Formula B or hydrolyzed and condensed products thereof, where: X is an organofunctional group; each R1 is a divalent linear, branched or cyclic organic group of 1 to about 12 carbon atoms optionally containing one or more hetero atoms; each R2 is independently an alkyl, aryl, alkaryl or aralkyl group of 1 to about 16 carbon atoms, optionally containing one or more halogen atoms; each R3 is independently an alkyl group of 1 to about 12 carbon atoms; a subscript is 0 or 1, b subscript is 0, 1 or 2 and a + b is 0, 1 or 2; and, the amount of alkoxysilane of Formula A when a subscript is 0 or 1, b subscript is 0, 1 or 2 and a + b is 2 is 0 to about 25 weight percent of the coating composition, a amount of alkoxysilane of Formula A when a + b is 0 is 0 to about 15 weight percent of the coating formation composition, the combined amounts of alkoxysilane of Formula A in which a subscript is 0 or 1, b subscript is 0 or 1 and a + b is 1 and the alkoxysilane of Formula B is about 8 to about 40 weight percent of the coating formation composition, and the total amount of alkoxysilane of Formulas A and B does not exceed about 50 weight percent of the coating formation composition; (ii) at least one metal oxide in particulate form, the amount of metal oxide being about 5 to about 50 weight percent of the coating formation composition; (iii) at least one water-miscible organic solvent; (iv) at least one acid hydrolysis catalyst; (v) water; and (vi) optionally, at least one condensation catalyst, the coating formation composition having a viscosity within the range of about 3.0 to about 7.0 cStks at 25 ° C. 2. Coating formation composition according to claim 1, CHARACTERIZED by the fact that the total amount of alkoxysilane of Formulas A and B does not exceed about 45 weight percent of the coating formation composition. Coating formation composition according to claim 1, CHARACTERIZED by the fact that the total amount of alkoxysilane of Formulas A and B does not exceed about 40 weight percent of the coating formation composition. 4. Coating formation composition according to any of claims 1 to 3, CHARACTERIZED by the fact that in the alkoxysilane of Formula A, a is 1 and organofunctional group X is mercapto, acyloxy, glycidoxy, epoxy, epoxy, hexyl group, epoxycyclohexylethyl, hydroxy, episulfide, acrylate, methacrylate, ureide, thioureide, vinyl, allyl, -NHCOOR4 or -NHCOSR4 in which R4 is a monovalent hydrocarbyl group containing from 1 to about 12 carbon atoms, thiocarbamate group, ditiocarbamate, ditiocarbamate, ditiocarbamate, , thioether, disulfide, trisulfide, tetrasulfide, pentasulfide, hexasulfide, polysulfide, xanthate, trithiocarbonate, dithiocarbonate or isocyanurate or another group -Si (OR3) where R3 is as previously defined. Coating formation composition according to any of claims 1 to 4, CHARACTERIZED by the fact that in the alkoxysilane of formula B, R1 is a divalent hydrocarbon group containing at least one heteroatom selected from the group consisting of O, S and NR4 in which R4 is hydrogen or an alkyl group of 1 to about 4 carbon atoms. 6. Coating formation composition according to any of claims 1 to 5, CHARACTERIZED by the fact that at least one alkoxysilane (i) is selected from at least one element of the group consisting of Formula A trialkoxysilane in which one subscript is 0 or 1, b subscript is 0 or 1 and a + b is 1, trialoxoxysilane of Formula B, and mixtures of trialcoxysilanes of Formulas A and B. Coating formation composition according to any of claims 1 to 6, CHARACTERIZED by the fact that it comprises an alkoxysilane (i) selected from at least one element of the group consisting of Formula A dialkoxysilane in which a subscript is 0 or 1, subscript b is 0, 1 or 2 and a + b is 2, a tetra-alkoxysilane of Formula B where each of the a and b subscripts is 0 and mixtures of dialkoxysilane (s) and tetra-alkoxysilane (s) of the Formulas A and B. 8. Coating composition according to any of claims 1 to 7, CHARACTERIZED by the fact that the trialoxysilane of Formula A is at least one element selected from the group consisting of methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, etiltripropoxissilano, n-propyltrimethoxysilane, n-propyltriethoxysilane, n propiltripropoxissilano, n-propiltributoxissilano, n-butiltrimetoxissilano, isobutiltrimetoxissilano, n-pentiltrimetoxissilano, n-hexiltrimetoxissilano, isoociltrietoxissilano, vinyltrimethoxysilane, vinyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, octiltrimetoxissilano, trifluoropropiltrimetoxissilano, 3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane and 3-glycidoxypropyltriethoxysilane, and where Formula B trialcoxysilane is at least one element selected from the group consisting of 1,2-bis (trimethoxysilyl) ethane, 1,2-bis (triethoxysilyl) ethane, bis (trimethoxysilylpropyl) disulfide, bis (triethoxysilylpropyl) disulfide, bix (trimethoxysilylpropyl) tetrasulfide, bis (triethoxysilylpropyl) tetrasulfide, bis (3-triethoxysilpropyl) amine and bis (3-trimethoxysilpropyl). Coating-forming composition according to any of claims 1 to 8, CHARACTERIZED by the fact that the metal oxide (ii) is a colloidal suspension of at least one metal oxide selected from the group consisting of silica, alumina , titania, ceria, tin oxide, zirconia, antimony oxide, indium oxide, iron oxide, titania doped with iron oxide and / or zirconia and rare earth oxide. 10. Coating formation composition according to any of claims 1 to 9, CHARACTERIZED by the fact that the metal oxide (ii) is selected from a mixture of alumina and silica. 11. Coating formation composition according to any of claims 1 to 10, CHARACTERIZED by the fact that the metal oxide (ii) is selected from a mixture of alumina and silica, wherein said mixture has a weight ratio from alumina to silica (Al2O3 / SiO2) from 1:99 to 99: 1, preferably from 5:95 to 90:10, more preferably 5:95 to 75:25. 12. Coating formation composition according to any of claims 1 to 8, CHARACTERIZED by the fact that the metal oxide (ii) is selected from silica modified with alumina. 13. Coating formation composition according to any of claims 1 to 12, CHARACTERIZED by the fact that the water-miscible solvent (iii) is at least one element selected from the group consisting of alcohol, glycol, glycol ether and ketone . Coating formation composition according to any of claims 1 to 13, CHARACTERIZED by the fact that the at least one acid hydrolysis catalyst (iv) is at least one element selected from the group consisting of sulfuric acid, hydrochloric acid , acetic acid, propanoic acid, 2-methyl propanoic acid, butanoic acid, pentanoic acid (valeric acid), hexanoic acid (caproic acid), 2-ethylhexanoic acid, heptanoic acid (enanic acid), hexanoic acid, octanoic acid (caprylic acid) ), oleic acid, linoleic acid, cyclohexanecarboxylic acid, cyclohexylacetic acid, cyclohexenecarboxylic acid, benzoic acid, benzeneacetic acid, propanedioic acid (malonic acid), butanedioic acid (succinic acid), hexanedioic acid (adipic acid), 2-butenedioic acid (maleic acid), lauric acid, stearic acid, myristic acid, palmitic acid, isoanoic acid, versatic acid and amino acid, and in which the coating-forming composition also contains at least one condensation catalyst (vi) selected from the group consisting of tetrabutylammonium carboxylates of the formula [(C4H9) 4N] + [OC (O) -R5] - in which R5 is selected from the group consisting of hydrogen, groups alkyl containing from 1 to about 8 carbon atoms and aromatic groups containing from 6 to about 20 carbon atoms. 15. Coating formation composition according to any of claims 1 to 14, CHARACTERIZED by the fact that the condensation catalyst (vi) is at least one element selected from the group consisting of tetra-n-butylammonium acetate, tetra- n-butylammonium formate, tetra-n-butylammonium benzoate, tetra-n-butylammonium-2-ethylhexanoate, tetra-n-butylammonium-p-ethylbenzoate, tetra-n-butylammonium propionate and TBD-acetate (1,5,7-triazabicyclo [4.4.0] dec-5-ene (TBD)). 16. Coating formation composition according to any of claims 1 to 15, CHARACTERIZED by the fact that it has a viscosity within the range of about 4.0 to about 5.5 cStks at 25 ° C. 17. Coating formation composition according to any of claims 1 to 11 and 13 to 16, obtained by the process, CHARACTERIZED by the fact that it comprises: a) cooling of a mixture of alkoxysilane (i) and acid hydrolysis catalyst ( iv); b) adding metal oxide (ii) and water (vi) to the cooled mixture of step (a); c) adding water-miscible solvent (iii) and additional acid hydrolysis catalyst (iv) to the mixture resulting from step (b); d) aging the mixture resulting from step (c) under elevated temperature conditions and for a period of time determined to provide a curable coating formation composition having a viscosity within the range of about 3.0 to about 7.0 cStks at 25 ° C; and e) optionally adding the condensation catalyst (vi) in, during or after any of the previous steps. 18. Coating formation composition according to claim 17, CHARACTERIZED by the fact that the metal oxide (ii) is as defined in claims 9 or 10. 19. Coating formation composition according to any of claims 1 to 8 or 11 to 16, obtained by the process, CHARACTERIZED by the fact that it comprises: a) cooling of a mixture of the metal oxide (ii) and the catalyst of acid hydrolysis (iv) preferably up to a temperature of about -20oC to about 15oC, preferably of about -10oC to about 10oC, more preferably about 0 to about 10oC, b) addition of alkoxysilane ( i) the cooled mixture from step (b); c) allowing the mixture obtained in step c) to reach room temperature (about 25 ° C), d) adding at least one water-miscible organic solvent (iii) and, optionally, the condensation catalyst (vi) and optionally one or more other optional components (vii) to the mixture obtained in step d) to obtain a composition having a viscosity within the range of about 3.0 to about 7.0 cStks at 25 ° C. 20. Coating formation composition according to claim 19, CHARACTERIZED by the fact that the metal oxide (ii) is as defined in claim 12. 21. Coating formation composition according to any of claims 17 to 20, CHARACTERIZED by the fact that it has a viscosity of about 4.0 to about 5.5 cStks at 25 ° C. 22. Coating formation composition according to any of claims 17 to 21, CHARACTERIZED by the fact that alkoxysilane (i) is at least one element selected from the group consisting of Formula A trialkoxysilane in which a subscript is 0 or 1, subscript b is 0 or 1 and a + b is 1, Formula B trialcoxysilane and mixture of Formulas A and B trialcoxysilanes. 23. Coating formation composition according to any of claims 17 to 21, CHARACTERIZED by the fact that alkoxysilane (i) is at least one element selected from the group consisting of Formula A dialkoxysilane in which a subscript is 0 or 1 , subscript b is 0, 1 or 2 and a + b is 2, tetra-alkoxysilane of Formula B where each of the subscripts a and b is 0 and mixtures thereof. 24. Coating formation composition according to any of claims 17 to 22, CHARACTERIZED by the fact that the trialcoxysilane of Formula A is at least one element selected from the group consisting of methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltripropoxysilane, -propiltrimetoxissilano, n-propyltriethoxysilane, n propiltripropoxissilano, n-propiltributoxissilano, n-butiltrimetoxissilano, isobutiltrimetoxissilano, n-pentiltrimetoxissilano, n-hexiltrimetoxissilano, isoociltrietoxissilano, vinyltrimethoxysilane, vinyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, octiltrimetoxissilano, trifluoropropiltrimetoxissilano, 3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane , 3-mercaptopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane and 3-glycidoxypropyltriethoxysilane and where the Formula B trialcoxysilane is at least one element selected from the group consisting of 1,2-bis (trimethoxys silyl) ethane, 1,2-bis (triethoxysilyl) ethane, bis (trimethoxysilylpropyl) disulfide, bis (triethoxysilylpropyl) disulfide, bix (trimethoxysilylpropyl) tetrasulfide, bis (triethoxysilylpropyl) tetrasulfide, bis (3-triethoxysilylpropyl) amine and bis (3 trimethoxysilylpropyl) amine. 25. Coating formation composition according to any of claims 17 to 18, CHARACTERIZED by the fact that the metal oxide (ii) is at least one element selected from an aqueous colloidal suspension of at least one metal oxide selected from the group consisting of silica, alumina, titania, ceria, tin oxide, zirconia, antimony oxide, indium oxide, iron oxide, titania doped with iron oxide and / or zirconia and rare earth oxide, in which the water-miscible solvent (iii) is at least one element selected from the group consisting of alcohol, glycol, glycol ether and ketone, where the acid hydrolysis catalyst (iv) is at least one element selected from the group consisting of sulfuric acid, hydrochloric acid, acetic acid, propanoic acid, 2-methyl propanoic acid, butanoic acid, pentanoic acid (valeric acid), hexanoic acid (caproic acid), 2-ethylhexanoic acid, heptanoic acid (enanthic acid), hexanoic acid, octanoic acid (caprylic acid), oleic acid , linoleic acid, cyclohexanecarboxylic acid, cyclohexylacetic acid, cyclohexenecarboxylic acid, benzoic acid, benzenoacetic acid, propanedioic acid (malonic acid), butanedioic acid (succinic acid), hexanedioic acid (adipic acid), 2-butene acid dioic (maleic acid), lauric acid, stearic acid, myristic acid, palmitic acid, isoanoic acid, versatic acid and amino acids, and wherein the coating formation composition also comprises at least one condensation catalyst (vi) selected from the group consisting of tetrabutylammonium carboxylates of the formula [(C4H9) 4N] + [OC (O) -R5] - in which R5 is selected from the group consisting of hydrogen, alkyl groups containing from 1 to about 8 carbon atoms and aromatic groups containing about 6 to about 20 carbon atoms. 26. Coating formation composition according to any of claims 19 to 20, CHARACTERIZED by the fact that the metal oxide (ii) is selected from silica modified with alumina, in which the water-miscible solvent (iii) is at least at least one element selected from the group consisting of alcohol, glycol, glycol ether and ketone, where the acid hydrolysis catalyst (iv) is at least one element selected from the group consisting of sulfuric acid, hydrochloric acid, acetic acid, propanoic acid , 2-methyl propanoic acid, butanoic acid, pentanoic acid (valeric acid), hexanoic acid (caproic acid), 2-ethylhexanoic acid, heptanoic acid (enanthic acid), hexanoic acid, octanoic acid (caprylic acid), oleic acid, oleic acid linoleic, cyclohexanecarboxylic acid, cyclohexylacetic acid, cyclohexenecarboxylic acid, benzoic acid, benzeneacetic acid, propanedioic acid (malonic acid), butanedioic acid (succinic acid), hexanedioic acid (adipic acid o), 2-butenedioic acid (maleic acid), lauric acid, stearic acid, myristic acid, palmitic acid, isoanoic acid, versatic acid, lauric acid, stearic acid, myristic acid, palmitic acid, isoanoic acid and amino acids, and in which the coating formation composition also comprises at least one condensation catalyst (vi) selected from the group consisting of tetrabutylammonium carboxylates of the formula [(C4H9) 4N] + [OC (O) -R5] - in which R5 is selected from group consisting of hydrogen, alkyl groups containing from 1 to about 8 carbon atoms and aromatic groups containing from 6 to about 20 carbon atoms. 27. Coating formation composition according to any of claims 17 to 18, CHARACTERIZED by the fact that in step (a), the mixture is cooled to a temperature of about -20oC to about 15oC. Coating formation composition according to any of claims 17 to 18, CHARACTERIZED by the fact that in step (a), the mixture contains from about 10 to about 50 weight percent of the total amount of catalyst acid hydrolysis (iv), with the balance of the acid hydrolysis catalyst (iv) being added in step (c). 29. Coating formation composition according to any of claims 17 to 18, CHARACTERIZED by the fact that in step (e), the mixture resulting from step (d) is aged at a temperature of about 20 C to about 100 oC for a period of about 1 to about 60 days. 30. Process for coating a metal surface to impart corrosion resistant and / or abrasion resistant properties to it, CHARACTERIZED by the fact that it comprises the application of the coating formation composition according to any of claims 1 to 29, to an uncoated or pre-coated metal surface for which corrosion resistance and / or abrasion resistance is desired and curing of the coating formation composition applied to provide a corrosion resistant and / or resistant to coating abrasion on it. 31. Process according to claim 30, CHARACTERIZED by the fact that the coating formation composition is applied to an anodized aluminum, bulk aluminum, magnesium, steel, copper, bronze or alloy surface thereof, a metallized surface or a metal having at least one protective layer. 32. Process for coating a metal surface to impart corrosion resistant and / or abrasion resistant properties to it, CHARACTERIZED by the fact that it comprises the application of a coating formation composition obtained by the process, according to any from claims 17 to 26, to an uncoated or pre-coated metal surface for which corrosion resistance and / or abrasion resistance is desired and curing of the coating formation composition applied to provide a corrosion resistant coating and / or abrasion resistant on it. 33. Process according to claim 32, CHARACTERIZED by the fact that the coating formation composition is applied to an anodized aluminum, bulk aluminum, magnesium, steel, copper, bronze or alloy surface thereof, a metallized surface or a part of metal having at least one protective layer. 34.Surface coated with a metal, CHARACTERIZED by the fact that it comprises the corrosion resistant and / or abrasion resistant coating prepared by the process, according to claim 30.